Análise tribo-termodinâmica da aplicação de nanopartículas de Al2O3 como aditivo lubrificante em compressor hermético de refrigeração

The thermodynamic performance of a refrigeration system can be improved by reducing the compression work by a particular technique for a specific heat removal rate. This study examines the effect of small concentrations of Al2O3 (50 nm) nanoparticles dispersion in the mineral oil based lubricant on the: viscosity, thermal conductivity, and lubrication characteristics as well as the overall performance (based on the Second Law of Thermodynamics) of the refrigerating system using R134a or R600a as refrigerants. The study looked at the influences of variables: i) refrigerant charge (100, 110, 120 and 130 g), ii) rotational speed of the condenser blower (800 and 1100 RPM) and iii) nanoparticle concentration (0.1 and 0.5 g/l) on the system performance based on the Taguchi method in a matrix of L8 trials with the criterion "small irreversibility is better”. They were carried pulldown and cycling tests according to NBR 12866 and NBR 12869, respectively, to evaluate the operational parameters: on-time ratio, cycles per hour, suction and discharge pressures, oil sump temperature, evaporation and condensation temperatures, energy consumption at the set-point, total energy consumption and compressor power. In order to evaluate the nanolubricant characteristics, accelerated tests were performed in a HFRR bench. In each 60 minutes test with nanolubricants at a certain concentration (0, 0.1 and 0.5 g/l), with three replications, the sphere (diameter 6.00 ± 0.05 mm, Ra 0.05 ± 0.005 um, AISI 52100 steel, E = 210 GPa, HRC 62 ± 4) sliding on a flat plate (cast iron FC200, Ra <0.5 ± 0.005 um) in a reciprocating motion with amplitude of 1 mm, frequency 20 Hz and a normal load of 1,96 N. The friction coefficient signals were recorded by sensors coupled to the HFRR system. There was a trend commented bit in the literature: a nanolubricant viscosity reduction at the low nanoparticles concentrations. It was found the dominant trend in the literature: increased thermal conductivity with increasing nanoparticles mass fraction in the base fluid. Another fact observed is the significant thermal conductivity growth of nanolubricant with increasing temperature. The condenser fan rotational speed is the most influential parameter (46.192%) in the refrigerator performance, followed by R600a charge (38.606%). The Al2O3 nanoparticles concentration in the lubricant plays a minor influence on system performance, with 12.44%. The results of power consumption indicates that the nanoparticles addition in the lubricant (0.1 g/L), together with R600a, the refrigerator consumption is reduced of 22% with respect to R134a and POE lubricant. Only the Al2O3 nanoparticles addition in the lubricant results in a consumption reduction of about 5%.

Análise tribo-termodinâmica da aplicação de nanopartículas de Al2O3 como aditivo lubrificante em compressor hermético de refrigeração

The thermodynamic performance of a refrigeration system can be improved by reducing the compression work by a particular technique for a specific heat removal rate. This study examines the effect of small concentrations of Al2O3 (50 nm) nanoparticles dispersion in the mineral oil based lubricant on the: viscosity, thermal conductivity, and lubrication characteristics as well as the overall performance (based on the Second Law of Thermodynamics) of the refrigerating system using R134a or R600a as refrigerants. The study looked at the influences of variables: i) refrigerant charge (100, 110, 120 and 130 g), ii) rotational speed of the condenser blower (800 and 1100 RPM) and iii) nanoparticle concentration (0.1 and 0.5 g/l) on the system performance based on the Taguchi method in a matrix of L8 trials with the criterion "small irreversibility is better”. They were carried pulldown and cycling tests according to NBR 12866 and NBR 12869, respectively, to evaluate the operational parameters: on-time ratio, cycles per hour, suction and discharge pressures, oil sump temperature, evaporation and condensation temperatures, energy consumption at the set-point, total energy consumption and compressor power. In order to evaluate the nanolubricant characteristics, accelerated tests were performed in a HFRR bench. In each 60 minutes test with nanolubricants at a certain concentration (0, 0.1 and 0.5 g/l), with three replications, the sphere (diameter 6.00 ± 0.05 mm, Ra 0.05 ± 0.005 um, AISI 52100 steel, E = 210 GPa, HRC 62 ± 4) sliding on a flat plate (cast iron FC200, Ra <0.5 ± 0.005 um) in a reciprocating motion with amplitude of 1 mm, frequency 20 Hz and a normal load of 1,96 N. The friction coefficient signals were recorded by sensors coupled to the HFRR system. There was a trend commented bit in the literature: a nanolubricant viscosity reduction at the low nanoparticles concentrations. It was found the dominant trend in the literature: increased thermal conductivity with increasing nanoparticles mass fraction in the base fluid. Another fact observed is the significant thermal conductivity growth of nanolubricant with increasing temperature. The condenser fan rotational speed is the most influential parameter (46.192%) in the refrigerator performance, followed by R600a charge (38.606%). The Al2O3 nanoparticles concentration in the lubricant plays a minor influence on system performance, with 12.44%. The results of power consumption indicates that the nanoparticles addition in the lubricant (0.1 g/L), together with R600a, the refrigerator consumption is reduced of 22% with respect to R134a and POE lubricant. Only the Al2O3 nanoparticles addition in the lubricant results in a consumption reduction of about 5%.

Contribuição ao estudo de treliças não lineares considerando efeitos térmicos

This work presents the numerical analysis of nonlinear trusses summited to thermomechanical actions with Finite Element Method (FEM). The proposed formulation is so-called positional FEM and it is based on the minimum potential energy theorem written according to nodal positions, instead of displacements. The study herein presented considers the effects of geometric and material nonlinearities. Related to dynamic problems, a comparison between different time integration algorithms is performed. The formulation is extended to impact problems between trusses and rigid wall, where the nodal positions are constrained considering nullpenetration condition. In addition, it is presented a thermodynamically consistent formulation, based on the first and second law of thermodynamics and the Helmholtz free-energy for analyzing dynamic problems of truss structures with thermoelastic and thermoplastic behavior. The numerical results of the proposed formulation are compared with examples found in the literature.

Necessary conditions for the emergence of homochirality via autocatalytic self-replication

We analyze a recent proposal for spontaneous mirror symmetry breaking based on the coupling of first-order enantioselective autocatalysis and direct production of the enantiomers that invokes a critical role for intrinsic reaction noise. For isolated systems, the racemic state is the unique stable outcome for both stochastic and deterministic dynamics when the system is in compliance with the constraints dictated by the thermodynamics of chemical reaction processes. In open systems, the racemic outcome also results for both stochastic and deterministic dynamics when driving the auto-catalysis unidirectionally by external reagents. Nonracemic states can result in the latter only if the reverse reactions are strictly zero: these are kinetically controlled outcomes for small populations and volumes, and can be simulated by stochastic dynamics. However, the stability of the thermodynamic limit proves that the racemic outcome is the unique stable state for strictly irreversible externally driven autocatalysis. These findings contradict the suggestion that the inhibition requirement of the Frank autocatalytic model for the emergence of homochirality may be relaxed in a noise-induced mechanism.

MRI-Guided Radiation Therapy: Investigating the Accuracy of Treatment Delivery

Purpose: To develop, evaluate and apply a novel high-resolution 3D remote dosimetry protocol for validation of MRI guided radiation therapy treatments (MRIdian® by ViewRay®). We demonstrate the first application of the protocol (including two small but required new correction terms) utilizing radiochromic 3D plastic PRESAGE® with optical-CT readout.

Methods: A detailed study of PRESAGE® dosimeters (2kg) was conducted to investigate the temporal and spatial stability of radiation induced optical density change (ΔOD) over 8 days. Temporal stability was investigated on 3 dosimeters irradiated with four equally-spaced square 6MV fields delivering doses between 10cGy and 300cGy. Doses were imaged (read-out) by optical-CT at multiple intervals. Spatial stability of ΔOD response was investigated on 3 other dosimeters irradiated uniformly with 15MV extended-SSD fields with doses of 15cGy, 30cGy and 60cGy. Temporal and spatial (radial) changes were investigated using CERR and MATLAB’s Curve Fitting Tool-box. A protocol was developed to extrapolate measured ΔOD readings at t=48hr (the typical shipment time in remote dosimetry) to time t=1hr.

Results: All dosimeters were observed to gradually darken with time (<5% per day). Consistent intra-batch sensitivity (0.0930±0.002 ΔOD/cm/Gy) and linearity (R2=0.9996) was observed at t=1hr. A small radial effect (<3%) was observed, attributed to curing thermodynamics during manufacture. The refined remote dosimetry protocol (including polynomial correction terms for temporal and spatial effects, CT and CR) was then applied to independent dosimeters irradiated with MR-IGRT treatments. Excellent line profile agreement and 3D-gamma results for 3%/3mm, 10% threshold were observed, with an average passing rate 96.5%± 3.43%.

Conclusion: A novel 3D remote dosimetry protocol is presented capable of validation of advanced radiation treatments (including MR-IGRT). The protocol uses 2kg radiochromic plastic dosimeters read-out by optical-CT within a week of treatment. The protocol requires small corrections for temporal and spatially-dependent behaviors observed between irradiation and readout.

Assessment of primary energy conversions of oscillating water columns. II. Power take-off and validations

This is the second part of the assessment of primary energy conversions of oscillating water columns (OWCs) wave energy converters. In the first part of the research work, the hydrodynamic performance of OWC wave energy converter has been extensively examined, targeting on a reliable numerical assessment method. In this part of the research work, the application of the air turbine power take-off (PTO) to the OWC device leads to a coupled model of the hydrodynamics and thermodynamics of the OWC wave energy converters, in a manner that under the wave excitation, the varying air volume due to the internal water surface motion creates a reciprocating chamber pressure (alternative positive and negative chamber pressure), whilst the chamber pressure, in turn, modifies the motions of the device and the internal water surface. To do this, the thermodynamics of the air chamber is first examined and applied by including the air compressibility in the oscillating water columns for different types of the air turbine PTOs. The developed thermodynamics is then coupled with the hydrodynamics of the OWC wave energy converters. This proposed assessment method is then applied to two generic OWC wave energy converters (one bottom fixed and another floating), and the numerical results are compared to the experimental results. From the comparison to the model test data, it can be seen that this numerical method is capable of assessing the primary energy conversion for the oscillating water column wave energy converters.

Primary wave energy conversions of oscillating water columns

This paper presents a study on the numerical simulation of the primary wave energy conversion in the oscillating water column (OWC) wave energy converters (WECs). The new proposed numerical approach consists of three major components: potential flow analysis for the conventional hydrodynamic parameters, such as added mass, damping coefficients, restoring force coefficients and wave excitations; the thermodynamic analysis of the air in the air chamber, which is under the assumptions of the given power take-off characteristics and an isentropic process of air flow. In the formulation, the air compressibility and its effects have been included; and a time-domain analysis by combining the linear potential flow and the thermodynamics of the air flow in the chamber, in which the hydrodynamics and thermodynamics/aerodynamics have been coupled together by the force generated by the pressurised and de-pressurised air in the air chamber, which in turn has effects on the motions of the structure and the internal water surface. As an example, the new developed approach has been applied to a fixed OWC device. The comparisons of the measured data and the simulation results show the new method is very capable of predicting the performance of the OWC devices.

Phonon anharmonicity and negative thermal expansion in SnSe

The anharmonic phonon properties of SnSe in the Pnma phase were investigated with a combination of experiments and first-principles simulations. Using inelastic neutron scattering (INS) and nuclear resonant inelastic X-ray scattering (NRIXS), we have measured the phonon dispersions and density of states (DOS) and their temperature dependence, which revealed a strong, inhomogeneous shift and broadening of the spectrum on warming. First-principles simulations were performed to rationalize these measurements, and to explain the previously reported anisotropic thermal expansion, in particular the negative thermal expansion within the Sn-Se bilayers. Including the anisotropic strain dependence of the phonon free energy, in addition to the electronic ground state energy, is essential to reproduce the negative thermal expansion. From the phonon DOS obtained with INS and additional calorimetry measurements, we quantify the harmonic, dilational, and anharmonic components of the phonon entropy, heat capacity, and free energy. The origin of the anharmonic phonon thermodynamics is linked to the electronic structure.

Chemical composition of ocean manganese nodules from the Pacific Ocean using different techniques

Mineralogical and chemical analyses performed on 67 ferromanganese nodules from widely varying locations and depths within the marine environment of the Pacific Ocean indicate that the minor element composition is controlled by the mineralogy and that the formation of the mineral phases is depth dependent. The pressure effect upon the thermodynamics or kinetics of mineral formation is suggested as the governing agent in the depth dependence of the mineralogy. The minor elements, Pb and Co, appear concentrated in the dMnO2 phase, whereas Cu and Ni are more or less excluded from this phase. In the manganites, Pb and Co are relatively low in concentration, whereas Cu and Ni are spread over a wide range of values. The oxidation of Pb and Co from divalent forms in sea water to higher states can explain their concentration in the dMnO2 phase.

Bubble Growth From First Principals

We consider the simplest relevant problem in the foaming of molten plastics, the growth of a single bubble in a sea of highly viscous Newtonian fluid, and without interference from other bubbles. This simplest problem has defied accurate solution from first principles. Despite plenty of research on foaming, classical approaches from first principles have neglected the temperature rise in the surrounding fluid, and we find that this oversimplification greatly accelerates bubble growth prediction. We use a transport phenomena approach to analyze the growth of a solitary bubble, expanding under its own pressure. We consider a bubble of ideal gas growing without the accelerating contribution from mass transfer into the bubble. We explore the roles of viscous forces, fluid inertia, and viscous dissipation. We find that bubble growth depends upon the nucleus radius and nucleus pressure. We begin with a detailed examination of the classical approaches (thermodynamics without viscous heating). Our failure to fit experimental data with these classical approaches, sets up the second part of our paper, a novel exploration of the essential decelerating role of viscous heating. We explore both isothermal and adiabatic bubble expansion, and also the decelerating role of surface tension. The adiabatic analysis accounts for the slight deceleration due to the cooling of the expanding gas, which depends on gas polyatomicity. We also explore the pressure profile, and the components of the extra stress tensor, in the fluid surrounding the growing bubble. These stresses can eventually be frozen into foamed plastics. We find that our new theory compares well with measured bubble behavior.

Heat Transfer in an Airfoil Shaped Strut

The heat transfer from a hot primary flow stream passing over the outside of an airfoil shaped strut to a cool secondary flow stream passing through the inside of that strut was studied experimentally and numerically. The results showed that the heat transfer on the inside of the strut could be reliably modeled as a developing flow and described using a power law model. The heat transfer on the outside of the strut was complicated by flow separation and stall on the suction side of the strut at high angles of attack. This separation was quite sensitive to the condition of the turbulence in the flow passing over the strut, with the size of the separated wake changing significantly as the mean magnitude and levels of anisotropy were varied. The point of first stall moved by as much as 15% of the chord, while average heat transfer levels changed by 2-5% as the inlet condition was varied. This dependence on inlet conditions meant that comparisons between experiment and steady RANS based CFD were quite poor. Differences between the CFD and experiment were attributed to anisotropic and unsteady effects. The coupling between the two flows was shown to be quite low - that is to say, heat transfer coefficients on both the inner and outer surfaces of the strut were relatively unaffected by the temperature of the strut, and it was possible to predict the temperature on the strut surface quite reliably using heat transfer data from decoupled tests, especially for CFD simulations.

Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.